Synthetic organic textile fiber with improved, durable, soft, lubricated feel

ABSTRACT

Process comprising treating synthetic organic textile fibers with a finishing composition that is (1) a mixture of a polyepoxide and an aminosiloxane, (2) a mixture of an epoxysiloxane and a polyamine, or (3) a mixture of an epoxysiloxane and an aminosiloxane, and thereafter curing said composition by subjection to elevated temperature. The treated fibers possess a durable, soft, lubricated feel.

United States Patent Trchenor [4 Apr. 11, 1972 54] SYNTHETIC ORGANICTEXTILE FIBER 3,220,878 11/1965 Pines ..117/123 WITH IMPROVED, DURABLE,SOFT, g,52,822 541966 Marzlocchi it] ...117/216/G2N 99,16 1 196 Embemet08 4 LUBRICATED FEEL 3,303,048 2/1967 Cooper et a1. 117/135 5 [72]Inventor: Robert L. Tichenor, Waynesboro, Va. 3,335,105 7/1964 Burnthallet al.. .....260/29 2 1 i 1 [73] Asslgneei 2 3,233,120 211323 1112: 111,...1 170 38. 8 1 1 wllmmgwn 3,488,217 1/1970 Ryan ..117/138.8 22 Filed;,197 3,511,699 5/1970 Johnson et a1. ....117/161 ZB 3,516,964 6/1970Patterson ....260/348 SC 1 1 Appl- N6: 17,205 2,819,245 1/1958 Shorr....260/824 EP Related Us. Application Data 3,247,280 4/1966 Kanner..260/824 EP [63] Continuation-impart 6r Ser. NO. 813,280, Apr. 3,FOREIGN PATENTS 0R APPLICATIONS 1969, abandoned- 630,016 10/1961 Canada.117/161 ZB 1,077,190 7/ 1967 Great Britain [52] US. Cl. ..ll7/138.8 A,8/115.6, 117/1388 UA,

117/1388 N, 117/1383 F, 117/1395 A, 117/161 Primary Examiner-William D.Martin ZA, 1 17/161 23, 252/85, 260/824 EP Assistant ExaminerRa1phHusack {51] Int. Cl. Attorney-John [58] Field of Search ..117/138.8 UA,138.8 F, 138.8 N,

117/1395 CQ, 139.5 A, 161 ZA, 161 ZB; 8/115.'6; [57] ABSTRACT 252/86;260/348 SC, 825, 824 EP, 29.2 M

Process comprlsmg treatmg synthetlc orgamc textile fibers [56]References Cited with a finishing composition that is (1) a mixture of apolyepoxide and an aminosiloxane, (2) a mixture of an epox- UNITEDSTATES PATENTS ysiloxane and a polyamine, or (3) a mixture of anepoxysiloxane and an aminosiloxane, and thereafter curing said composi-2,557,803 7/1951 Sommer ..260/448.2 tion by subjection to elevatedtemperature The treated fibers 2,762,823 9/1953 Speter ..260/448.2possess a durable Soft lubricated feeL 3,055,774 9/1962 Gllkey et a1..117/135.5 3,166,527 1/1965 Ender ..260/825 5 Claims, 3 Drawing FiguresUNIODIFIED iACRYLONITRILE ACRYLONITRILE POLYMER FIBERS P 1151111110 111AHINOSILOXANE-EPOXY mm H ERS 00111 05111011 00/111110.\ 0,45

040 ALPACA},

ACRYLONITRILE POLYMER FIBERS BEARING A PRIOR ART $1111 HYDROGEN FRICIIONACRYLONITRILE POLYMER FIBERS BEARING AN EPOXYSILICONE 1,4- 020 E.011111110110111115 001111110 \5- 1 10 10 10 10 10' 10 SLIDING SPEED(Cl/SEC.)

PATENTEDAPR 1 1 I972 SHEET 1 OF 3 FIG...

if //|02CM./SEC

/ \ACRYLONITRILE POLYMER FIBERS BEARING AMINOSILOXANE-EPOXY composmoucomm:

I.6X I03 CMJSEC.

5 0 a. m 222:: E PZEQIHIQQ lo" |o suomc SPEED (cm/5m) INVENTOR ROBERT L.TICHENOR ATTORNEY PATENTEDAPR 11 I972 3.655.420

SHEET 3 0F 3 0.50 POLYETHYLENE TEREPHA E FIBERS BEARING AN AMISILOXANE-EPOXY COMPOSIT- ION 001mm; 1 0.45 E 2 E 0.40 '5 50.35UNMODIFIED POLYETHYLENE o TEREPHTHALATE FIBERS W I0 l0" |0 l0 l0 SLIDINGSPEED (CM! SEC) iNVENTOR ROBERT L'. TICHENOR ATTORNEY SYNTHETIC ORGANICTEXTILE FIBER WITH IMPROVED, DURABLE, SOFT, LUBRICATED FEELCROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part ofapplication Ser. No. 5 813,280, filed Apr. 3, 1969, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to synthetic organictextile fibers, and, more particularly, to treating such fibers toprovide a durable, soft, lubricated feel.

It is desired to provide a technique for producing textile fibers havinga durable, soft, lubricated feel similar to that possessed by cashmereand other luxury animal fibers such as alpaca and mohair. Some temporaryfinishes have been used to impart the cashmere feel to fibers, but thesefinishes are removed by washing. Thus, condensation products of longchain fatty acids, acid chlorides, or acid anhydrides with alkanolaminesyield finishing compositions which impart a soft, slick hand to fibers,but which are not fast to washing.

Somewhat more durable and otherwise satisfactory finishes are thesilicones. These are made by hydroylsis of various mixtures of mono-,di-, and tri-alkyl chlorosilanes followed by condensation in which wateris split out from two or more different molecules. The resultingpolymers impart a pleasant, lubricated feel to synthetic organic fibers.If the silicone is made from an alkyl hydrogen-chlorosilane so that thepolymer will contain some hydrogen groups bonded directly to silicon,(i.e., silyl hydrogen), the finish will be somewhat durable becausecrosslinking will occur as the silicon hydrogen groups are hydrolyzed tosilanol and these condense to form interchain bridges, But even thesesilicones will not resist repeated scouring.

Greatly improved scouring resistance is provided by finishes applied asaqueous dispersions of polyepoxides and of siloxanes containing silylhydrogen atoms. However, these dispersions are not storage-stable, andcan produce nonuniform results in commercial practice, becausecross-linking reactions commence prior to application especially in thepresence of acidic, alkaline, or metallic ion impurities, or when thetemperature of the dispersion is elevated.

Improved scouring resistance is also provided by finishes knownheretofore made from reactive siloxanes containing free amine groups anda serially-applied fixative containing diisocyanate groups or othergroups complementary to amines. However, the serial application processis expensive and complex, imposes requirements of immiscibility betweenthe two solutions or dispersions, and is limited to such mixing ofsiloxane and fixative as can occur after application.

The pleasant, lubricated feel imparted to synthetic organic fibers bysilicone finishes has been attributed to the lower coefficient offriction of fibers coated with the finish with respect to the uncoatedfibers. While the synthetic organic fibers coated with the siliconefinishes available hitherto have been regarded as more similar to theluxury animal fibers than are the uncoated fibers, a need has been feltfor such fibers having a highly durable finish still more closelyresembling the characteristics of the luxury animal fibers. Anadditional need is for a simple process for applying durable siliconefinishes onto textile fibers.

SUMMARY OF THE lNVENTION The present invention broadly provides aprocess for treating synthetic organic textile fibers with a finishingcomposition that is (1) a mixture of a polyepoxide and an aminosiloxane,(2) a mixture of an epoxysiloxane and a polyamine, or (3) a mixture ofan epoxysiloxane and an aminosiloxane. Specifically, this inventionprovides a process for treating synthetic organic textile fiberscomprising applying to said fibers a finishing composition andthereafter curing said composition by subjection to elevated temperaturesaid composition being selected from the group consisting of:

l. a mixture of about 0.05 to 3 parts by weight of a soluble epoxycompound having at least two epoxy groups per molecule, together with 1part by weight of a liquid aminosiloxane wherein there is one oxygenatom bridging each pair of neighboring silicon atoms and all othersilicon valences are bonded only to carbon atoms, said aminosiloxaneconsisting essentially of repeating units of the formulae:

El Li 1 0S'1 and I L .1 y L J EE.

R is a lower alkyl or aryl group,

R is hydrogen or a lower alkyl or aryl group,

A is an alkylene group having two to five carbon atoms or an arylene orsubstituted arylene group having six to 10 carbon atoms, provided R andA are selected so that not more than one aromatic ring is attacheddirectly to the amino nitrogen atom,

said aminosiloxane containing at least 35 of said repeating wherein R"is a lower alkyl or aryl group,

A is an alkylene group having two to five carbon atoms or an arylene orsubstituted arylene group having six to 10 carbon atoms,

said epoxysiloxane having an epoxy group content of at least 1 percentbased on the total weight of said epoxysiloxane, and containing at least35 of said repeating units at least two of which have the formula:

together with 1 part by weight of an amine compound having at least twoamino groups per molecule, wherein each of said amino groups has atleast one hydrogen atom and not more than one aromatic ring attacheddirectly to the nitrogen atom; and 3. a mixture of about 0.05 to 20parts by weight of said epoxysiloxane together with 1 part by weight ofsaid aminosiloxane. The products of this invention possess a durable,soft, lubricated feel. The preferred products are fibers coated with across-linked (i.e., cured) composition of an aminosiloxane and apolyepoxide or epoxysiloxane, i.e., mixture (1) or (3) aminosiloxane anda polyepoxide or epoxy-siloxane is herein referred to as anaminosiloxane-epoxy composition.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings are plots of the frictioncoefficients, measured over a wide range of sliding speeds, of variousfibers. The shape of these plots has been found to correlate well withthe feel of fibers.

FIG. 1 is a plot of the friction coefficient, measured over a wide rangeof sliding speeds, of a sample of acrylonitrile polymer fibers coatedwith a preferred aminosiloxane-epoxy composition of this invention.

FIG. 2 is a plot of the sample shown in FIG. 1, superimposed oncorresponding plots of samples of alpaca and mohair, untreated fibers ofacrylonitrile polymer, fibers of acrylonitrile polymer coated with anepoxysiloxane-polyamine composition, and fibers of acrylonitrile polymercoated with a certain cured siloxane composition of the prior art.

FIG. 3 is a plot of samples of untreated polyethylene terephthalatefibers and polyethylene terephthalate fibers treated with anaminosiloxane-epoxy composition of this invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The process of this inventionbroadly comprises treating synthetic organic textile fibers with afinishing composition that is (I) a mixture of a polyepoxide and anaminosiloxane, (2) a mixture of an epoxysiloxane and a polyamine, or (3)a mixture of an epoxysiloxane and an aminosiloxane, and then heating thetreated fibers to cure the composition. This process produces textilefibers having a durable, soft, lubricated feel. The fiber finishesobtained in accordance with this invention are more durable than thefinishes obtained with the aminosiloxane or the epoxysiloxanes when usedalone. The aminosiloxane when used alone remains fluid and tacky, butwhen combined on the fiber with a polyepoxide or with an epoxysiloxaneit gives a soft, dry, slick hand to fibers and to fabrics made from thefibers. Similar synergistic results are obtained when the epoxysiloxaneis reacted with a polyamine.

All of the fiber finishes provided by the process of this in vention arehighly durable on the fiber and impart a pleasant, lubricated feel tothe fiber, as contrasted with the corresponding untreated fiber.Moreover, it has unexpectedly been found that synthetic organic fibersbearing an aminosiloxane-epoxy composition exhibit frictionalcharacteristics over a range of measuring speeds highly analogous to thefrictional characteristics of luxury animal fibers. Garments made of thefibers coated with the aminosiloxane-epoxy composition have a slick,soft feel markedly resembling the feel of garments made of luxury animalfibers. Surprisingly, the luxurious feel of garments of these fibers islong-lasting and persists throughout many laundering or dry cleaningcycles to which the garment is subjected during normal wear.

The character of the desirable frictional behavior of the syntheticorganic fibers bearing the aminosiloxane-epoxy composition will be moreclearly understood by reference to the accompanying figures, which areplots of the friction coefficients, measured over a wide range ofsliding speeds, of various fibers. Referring to FIG. 1, the coefficientof friction vs. sliding speed of an acrylonitrile terpolymer coated withan aminosiloxane-epoxy composition as described in Example XIII isplotted in the manner described hereinafter. It will be observed thatthe coefficient of friction curve of this fiber of the present inventionis characterized by a relatively low initial coefficient of friction;the curve dips slightly lower to a minimum (F,,,,,,) as the slidingspeed is increased, and then rises sharply and progressively as thesliding speed is increased to I cm./sec. (F This characteristic curve isobserved with other fibers of this invention having anaminosiloxaneepoxy composition coating.

It has been discovered that natural luxury animal fibers also havesimilar characteristic curves. Referring to FIG. 2, it will be seen thatwith alpaca and mohair, for example, the coefficient of friction isinitially relatively low, and dips slightly lower to a minimum as thesliding speed increases, and then rises sharply and progressively as thesliding speed is increased to cm./sec. Thus the coefficient of frictioncurve for the fiber of this invention (the curve shown in FIG. 2 is thesame as shown in FIG. 1) has the same characteristics as the naturalluxury fibers. By contrast, the coefficient of friction of an untreatedacrylonitrile polymer fiber shows a sharp progressive decrease as thesliding speed is increased, followed by only a modest rise, and at 100cm./sec., it is substantially lower than the initial value. Theacrylonitrile polymer fibers having other silicone-epoxy coatings (alsodescribed in Example XIII) also have markedly different coefiicient offriction curves as shown in FIG. 2.

Thus, FIG. 2 graphically illustrates the phenomenon that theacrylonitrile polymer fibers of the present invention coated with anaminosiloxane-epoxy composition feel to the human hand remarkablesimilar to the natural luxury fibers. Other silicone-epoxy compositions,including prior art compositions such as silyl hydrogen silicone-epoxycompositions, while providing considerable improvement in slicknesscompared to unmodified acrylonitrile polymer fibers, do notrealistically simulate the feel of the natural luxury fibers. FIG. 3illustrates the characteristic coefficient of friction curve of apolyethylene-terephthalate fiber treated in accordance with thisinvention as described in Example XVII.

Plots of the coefficient of friction of fibers, with respect to thesliding speed at which the measurement is made, are prepared as follows,except where otherwise specified. The test is carried out on staplefibers, and if the sample is submitted as a tow it is first cut tostaple fibers, preferably about 3 inches in length. A 2.0 g. sample ofthe staple fibers is carded by hand until the fibers are roughlyparallel and lie as a sheet on one of the sample cards. About 0.8 g. ofthis card web" is laid onto the surface of 2-inch wide, two-sidedpressure-sensitive tape, wrapped around a 2-inch diameter cardboardtube. Fibers are distributed axially around the tube to provide an evencoverage of the tape. Both ends of the fiber-covered tape are thenwrapped with narrow masking tape to anchor them more firmly.

An 0.25 g. portion of the carded fibers is then applied evenly to thesurface of a l 9-inch strip of one-sided pressuresensitive plastic tape.Since the tape is longer than the fibers, it is necessary to apply themin overlapping sheets, similar to application of shingles on a roof. Thelast half inch of each end of the tape is not covered with fibers and isfolded over to provide a reinforced anchorage for attachment to theapparatus to measure friction.

The staple-covered tape is draped over the staple-covered cylinder toprovide contact. The fibers at the interface contact each other atapproximately right angles. One end of the tape is attached to aforce-recording cell and the other is attached to a static load of 30 g.The cylinder is then rotated so that its circumference turns in thedirection from the forcerecording cell to the static load. Frictionforce data are recorded at sliding speeds ranging from l.6 l0' to l00cm./sec. depending on the rotating speed of the cylinder.

Friction coefficients are calculated using the following equation:

T Frictional force from strain gauge.

T Weight attached to staple-covered tape.

6 Contact angle of tape with cylinder in radians 3. 14.

F Friction coefficient.

A curve such as that shown in FIG. 1 is plotted and a mathematical ratiois calculated. This ratio, called the Objective Preference Index andabbreviated OPI is obtained by dividing the difference between the valueof the coefficient of friction at I00 cm./sec. (F and the value of thecoefficient of friction at the minimum point in the curve (F,,,,,,) bythe coefficient of friction at the minimum point (F,,,,,,) in accordancewith the equation:

0P1: (F100 min)/ min The present invention provides not only excellentfiber properties, but also marked process advantages. The components areintimately mixed before application, so that uniformity of the curedfinish is promoted and only a single application is made. Only twocomponents are required to be mixed together, which provides a simplemixing procedure. The aqueous dispersions of each component arerelatively storagestable, which promotes uniform results in commercialpractice. Finally, the curing step takes place rapidly and smoothly.

Aminosiloxanes suitable for use in this invention are characterized bybeing liquid and by having one oxygen atom bridging each pair ofneighboring silicon atoms, and all other silicon valences being bondedonly to carbon atoms. Thus, these aminosiloxanes have no silyl hydrogenatoms. These' aminosiloxanes are further characterized by consistingessentially of repeating units of the formulae:

R is a lower alkyl or aryl group, R is hydrogen or a lower alkyl or arylgroup, A is an alkylene group having two to five carbons or an arylenegroup or substituted arylene group having six to 10 carbons, provided Rand A are selected so that not more than one aromatic ring is attacheddirectly to the amino nitrogen atom. These aminosiloxanes contain bothtypes of repeating units, and contain a total of at least 35, preferably100 to 600, of these repeating units, at least two, preferably four to20, of which are units of the formula:

The degree of polymerization, i.e., the average total number of thesetwo repeating units per molecule, may be as high as L500 or even higher,provided the aminosiloxane is liquid. The lower alkyl groups in theseaminosiloxanes generally have one to four carbon atoms and the loweraryl groups generally have six to nine carbon atoms. Thus, R may be, forexample, methyl, ethyl, propyl, isopropyl or phenyl.

The repeating units, i.e., the

l HR .1

Lil L ll groups usually, but not always, occur randomly in thesecorporated in minor amounts to obtain branched compounds,

provided the compounds are liquid. The terminal end groups are usuallytrialkyl silyl groups, although other terminal end groups, such ashydroxyalkyl silyl groups or non-silicon-containing groups may be usedor there may be no terminal end 75 groups if the molecule is a ring.

If desired, additional amino groups may be present in the secondrepeating unit shown immediately above, for example, by substituting theR group to provide a unit of the formula:

l. I l A t W E Also, the R group may be replaced with additional A NHR'radicals. It is essential that the amino group be separated from eachother and from the silicon atoms by a connecting chain of at least twocarbon atoms.

A range of aminosiloxanes having variable weight percentages of aminegroups and variable degrees of polymerization are useful. Sinceaminosiloxanes with a high degree of polymerization are too viscous foreasy application, the preferred aminosiloxanes have a degree ofpolymerization of 100 to 600. The amine content may range from about 0.1percent to about 5 percent by weight. However, the amine content is fromabout 1 percent to about 3 percent by weight in the preferredaminosiloxanes, i.e., those used in preparing the optimum fiber productshaving the highest values for Objective Preference Index and thegreatest similarity to the natural animal fibers.

The soluble epoxy compounds used in this invention, also referred toherein as polyepoxides, are characterized by having at least two epoxygroups per molecule. These polyepoxides must not be significantlycross-linked, and thus, are further characterized by being soluble inany suitable solvent, such as absolute ethanol. This limitation does notimply that the polyepoxide must be soluble in the liquid medium, if any,in which the finishing compound is prepared. A diepoxide such asresorcinol diglycidyl ether is a suitable polyepoxide for use in thisinvention. Other suitable polyepoxides may be conveniently made byreacting epichlorhydrin with a polyhydroxy compound. One of thepreferred polyhydroxy compounds is glycerol. The preparation ofpolyepoxides from epichlorhydrin and glycerol is described in US. Pat.No. 2,872,428.

Other suitable polyhydroxy compounds include bisphenol A [i.e.,2,2-bis(4-hydroxy phenyl)propane]; 4,4'-dihydroxy diphenyl ether;4,4'-dihydroxy benzophenone; ethylene glycol; diethylene glycol; andpropylene glycols. Polyethylene oxide derivatives made by reactingethylene oxide with polyhydroxy compounds are also suitable for reactingwith epichlorhydrin. Thus, glycerol, ethylene glycol and the polyhydroxyaromatic derivatives listed above may first be reacted with from 1 to 20moles of ethylene oxide before reacting with epichlorhydrin. Furtherdetails of the preparation of suitable polyepoxides are given in US.Pat. No. 2,913,356.

When epichlorhydrin reacts with a hydroxy group, it forms an ether. Butthe epoxy group can react either with a hydroxy group or with anotherepoxy group so that the resulting products are polymers, rather thansimple epoxy ethers. For the purposes of this invention, it ispreferable to use low molecular weight polymers or the simple polyepoxycompounds. Polyepoxides with molecular weights of not over 5,000 areacceptable, but products in the range up to 1,000 are preferred. In mostcases, the products used are mixtures of various molecular weights andmay contain, and preferably do contain, some monomeric compounds havingtwo or more epoxide groups. Diglycidyl ether itself may be used.

It is preferred that the polyepoxides be water soluble or easily waterdispersible for convenience in using, but they can be used in organicsolvents, if desired.

Polymers containing epoxide groups and siloxane groups in the samemolecule, as disclosed in US. Pat. No. 3,055,774 to Gilkey et al., arealso useful in this invention. Disiloxanes such as1,3-bis-(3-glycidoxypropyl)tetramethyl-disiloxane or low molecularweight polysiloxanes containing more than one epoxide group per moleculewill yield slick fibers when crosslol F wherein R" is a lower alkyl oraryl group,

A is an alkylene group having two to five carbon atoms or an arylene orsubstituted arylene group having six to 10 carbon atoms.

These epoxysiloxanes contain both types of repeating units, and containa total of at least 35, preferably 100 to 600, of these repeating units,at least two, preferably four to 20 of which are units of the formula:

The epoxy group content of these epoxysiloxanes must be at least 1percent based on the total weight of the compound. The lower alkylgroups present in these epoxysiloxanes generally have one to four carbonatoms, for example, methyl, ethyl, propyl and isopropyl, and the loweraryl groups generally have six to nine carbon atoms, for example,phenyl. The repeating units, i.e., the

groups usually occur randomly in these epoxysiloxanes. Theepoxysiloxanes consist essentially of these two repeating units. Thelimitations concerning the maximum degree of polymerization, possibleother repeating units, and terminal end groups previously described withregard to the aminosiloxanes, also apply to these epoxysiloxanes.

If desired, additional epoxy groups may be present in the secondrepeating unit shown immediately above, for example, by substituting theR" group to provide a unit of the formula:

Additional epoxy groups may be added, provided the epoxy oxygen atomsare separated from each other and from silicon atoms by a connectingchain of at least two carbon atoms.

it is preferred that the epoxy siloxanes be water soluble or easilywater dispersible for convenience in using, but they can be used inorganic solvents or without solvents, if desired.

These epoxysiloxanes may be used in conjunction with the aminosiloxanesdescribed above or the amine compounds described below, to provideresults similar to that obtained with a combination of the aminosiloxaneand the described epoxy compound. in all cases improved and usefulslickness is obtained in the treated fiber as compared with theuntreated fiber. However, only when an aminosiloxane is employed as oneingredient to the fibers exhibit marked similarity to the natural luxuryanimal fibers, accompanied by high values for the Objective PreferenceIndex.

The amine compounds that are used in combination with the epoxysiloxanesin accordance with this invention are characterized by containingprimary and/or secondary amino groups and having at least two aminogroups per molecule. Examples of suitable amines are ethylene diamine,diethylene triamine, and other alkylene and arylene polyamines, N-alkylalkylene diamines, N-alkyl arylene diamines, diazines such as piperazine(hexahydropyrazine), amino-piperidines such as 2-aminohexahydropyridine. Primary amines are preferred over secondaryamines. Tertiary amines are not operable for use in this invention.

In mixtures of epoxysiloxanes and aminosiloxanes alone, the ratio ofepoxysiloxane to aminosiloxane may vary from about 0.05:] to about 20:]by weight, but in mixtures of aminosilox anes with epoxy compounds otherthan epoxy siloxanes and in mixtures of epoxysiloxanes with aminocompounds other than aminosiloxanes, the ratio of the nonsiloxanecompounds to the siloxane compounds may vary from about 0.05:] to about2:1 by weight, with the preferred ratios in all cases varying accord ingto the specific compounds employed. The amino-siloxaneepoxy compositionmay be prepared as solution in an organic solvent or, preferably, as anaqueous dispersion. The concentration of the composition in such asolution or dispersion may vary over a wide range, but a siloxaneconcentration of 2 to 20 percent by weight is generally adequate.Similarly, the amount of amino-siloxane-epoxy composition that isapplied onto the fibers may vary over a wide range, depending upon theparticular effect that is desired to be obtained. Generally about 0.1 to3 percent of siloxane, based on the dry weight of the fibers, will beadequate, and about 1.0 to 2 percent siloxane is usually preferred.

it is preferred that the amine-containing compound and theepoxide-containing compound be mixed only a short time before using. Theaminosiloxane or epoxysiloxane can be dispersed in water by means ofcationic or nonionic surface active agents. Suitable cation activeagents are stearyldimethylbenzyl ammonium chloride,stearoylcolaminoformylmethyl pyridinium chloride, and cetyltrimethylammonium chloride. A suitable nonionic type is an ether of nonylphenoland a polyalkylene glycol. After the components are dispersed and mixed,the resulting composition is applied to the fibers, preferably at roomtemperature, inasmuch as heating tends to cause premature cross-linkingand precipitation of the polymers.

when a solvent solution of finishing composition is desired, thesiloxane-containing compound is usually just dissolved in a suitablesolvent such as methylene chloride or other chlorinated hydrocarbon orethanol and then the epoxy compound is added. The organic solventsolution can then be applied to the fibers, or it may be added to watercontaining an emulsifying agent to form an emulsion of the siloxane andthe polyepoxide, and the resulting emulsion can be applied to thefibers. The product can also be made by applying solutions ordispersions of the two ingredients to the fiber in serial manner andthen curing them together on the fiber; although for economic reasonsand optimum product uniformity the ingredients are generally appliedtogether in solution or dispersion in accordance with the process of theinvention.

The product can also be made using salts of the aminosiloxane formed bymixing the aminosiloxane with a suficient quantity of a relativelyvolatile acid to neutralize all the amino groups. Neutralization of theaminosiloxane retards reaction between it and the polyepoxide. Thisretardation is particularly useful if it is desired to expose the coatedfibers to elevated temperatures, e.g., during crimping, beforeevaporating dispersing medium or solvent and curing the composition.

Removal of the volatile acid during evaporation and curing regeneratesthe aminosiloxane which then reacts readily with the polyepoxide.

All synthetic organic textile fibers, such as fibers of acrylonitrilepolymers, polyamides or polyesters, may be treated in accordance withthis invention. Fibers of acrylonitrile polymers, including homopolymersand copolymers, are especially benefited by this invention. Suitablepolyamide fibers for treatment in accordance with this invention arefibers of poly(hexamethylene (hexamethylene adipamide), polycaprolactam,and polyamides from bis(4- aminocyclohexyl)-methane and dicarboxylicacids containing six to 16 carbon atoms, such as poly(methylene-di- 1,4- cyclohexylene dodecane-diamide).

The composition used in this invention may be applied to fibers in theform of a tow or staple fibers, to filaments or spun yarn or even tofinished fabric. However, it is the prime object of the presentinvention to treat the fiber in the form of tow or staple where it wouldbe most economical and where the application can best be controlled togive uniform results. The treated tow or rope may conveniently be cutinto staple after impregnation and before curing.

After the finishing composition is applied to the fibers, any dispersingmedium or solvent is evaporated and the composition is cured bysubjection to elevated temperatures, usually within the range of 1 10 to160 C. for about to minutes. Lower temperatures may be used, at asacrifice of curing time, and in some instances higher temperatures mayeven be used. In every case the temperature should be low enough toprevent the fiber substrate from being deleteriously affected.

When this invention is used to treat fibers in the form of tow, it hasbeen found that best results are obtained if the tow to be treated isfree of oily finishes. The finishing composition made from the freeamine is preferably not applied before hot crimping because the heatwould cause premature polymerization of the mixture. The fibers may belubricated with a textile finish before crimping, if desired. Aftercrimping, the finishing composition may be applied without removing thecrimp.

After treatment in accordance with this invention, fibers have a soft,slick finish that is remarkably durable. This finish will not onlywithstand repeated wearing and washing or dry cleaning of garments madefrom treated fibers, but will withstand the rigorous scouring and dyeingoperations that are employed in the numerous steps involved inconverting tow into staple, then into yarn, and finally into fabrics andgarments. Moreover, it is surprising that this finish does not interferewith ordinary dyeing operations. These remarkable properties make thisinvention particularly useful for treating tow.

In addition to providing a durable, soft and lubricated feel to fibers,the process of this invention imparts other remarkable properties tofibers. For example, fibers finished by the process of this inventionyield fabrics which have less tendency to form pills on the surface.Also, the fabrics do not glaze as badly as do fabrics from untreatedfibers. Glazing is a condition where fibers are flattened and shapedinto a plane surface so that the fabrics have a shine. It is caused byhot pressing which fixes the fibers in place and they become slightlyadherent to each other. It is believed that the finishing compositiondecreases glazing by acting as a release agent, keeping the fibers fromsticking together and from being fixed in a plane surface. This freedomof motion is also believed responsible for some improvement in wrinkleresistance imparted by these agents to the fabric. The silicones aloneproduce similar benefits, but only temporarily. The effects are largelylost after one or two scourings or dry cleanings.

The following examples illustrate some of the preferred embodiments ofthis invention. In these examples, the siloxane retention percentage ismeasured by determining the silicon content in the respective fiber orfabric. This is done by fusing the sample of fiber or fabric withpotassium carbonate and forming with ammonium molybdate the yellowsilicomolybdate. The solution is then reduced with aminonaphtholsulfonic acid to yield molybdenum blue which is measured EXAMPLE 1 Eightparts of an aminosiloxane having the formula:

L a... lL

and having a degree of polymerization (i.e., the value of x+y which isabbreviated hereinafter as DP) of 500 and an NH content of 0.2 percent(aminosiloxane supplied by Union Carbide Corp., designated Y 5230) isstirred with 391 parts of methylene chloride, and 1.2 parts of apolyepoxide is added. This polyepoxide is a liquid mixture of linear andmoderately branched propylene ether polymers containing hydroxyl groups,chloromethyl groups, and an average of at least two epoxy groups permolecule; it is a condensation product of glycerine and epichlorhydrin;it has a pale yellow color; it has a viscosity of to 150 centipoises at25 C. (polyepoxide supplied by the Shell Chemical Corp., designatedEponite" The resulting solution is used to treat 52.2 pans of anacid-dyeable staple fiber made by dry spinning from solution indimethylformamide a polymer of 92.2 pans acrylonitrile, 5.4 parts methyl vinylpyridine, and 2.4 parts methyl acrylate. The treatment consists ofdipping the staple into the solution, removing and squeezing to 100percent pickup of the solution (i.e., the fibers picked up an amount ofcomposition equal to their own dry weight). This staple is then heatedfor 20 minutes at 70 C. and then 30 minutes at C. to fix the finish onthe fiber. The staple is next carded into a sliver. This sliver iscombined with 22.8 parts of an untreated, acid-dyeable, high-shrinkagesliver made from a polymer of 89.6 parts acrylonitrile, 4.7 parts methylvinyl pyridine and 5.7 parts methyl acrylate. The combined slivers arespun into a 6/ lcc (886 denier) yarn having 52 turns per inch twist(1.97 turns per cm.). The yarn is dyed in skein form for 1.75 hours atthe boil at a pH of 2.5 with Pontacyl Brilliant Blue RR (Dye Index No.42735). For each 100 parts of fiber, 2 parts of dyestuff, 3 parts sodiumsulfate and 0.5 part of leveling salt are dissolved in 200 parts waterand the pH adjusted to 2.5 with sulfuric acid. Dyeing is 1 hour 45minutes at the boil. After dyeing, the fiber is scoured at 70 C. using asodium alcohol sulfate detergent. It is rinsed and dried. The boilingcauses shrinking of the high shrinkage fiber yielding a bulky yarn andcauses the treated fibers to come to the surface. This yarn is next knitinto a novelty construction on a Passap Duomatic flat bed knittingmachine and tested for slickness before and after scouring and beforeand after mechanical, dry abrasion. The slickness is retained throughall these operations; that is, opening and carding of the staple,twisting and drafting of the sliver, skeining and dyeing of the yarn,knitting, scouring and abrading of the fabric.

EXAMPLE 11 Eight parts of a trimethyl silyl-end-capped, random copolymerof dimethyl siloxyl and methylaminopropylsiloxyl which is described bythe formula:

OSi(CHs)a having a DP of 200 and an Nl-l content of 1.82 percent (aminosiloxane supplied by Union Carbide Corp, designated Y 5455) is added to391 parts absolute ethanol with stirring and 1.2 parts polyepoxide isadded. Fifty parts of a basic-dyeable staple fiber spun from a polymerof 95.8 parts acrylonitrile and 4.2 parts sodium styrenesulfonate aredipped into the siloxane-epoxide solution then pressed to remove excesssolution, leaving 100 percent of solution on the fiber. The fiber isdried and heated 35 minutes at 130 C. to cause interaction of theaminosiloxane and the epoxide on the fiber. The treated fiber is nextcarded and formed into sliver A.

A bicomponent staple fiber with a homopolyrner of acrylonitrile on oneside and making up 75 percent of the filament, and a copolymer of 95parts acrylonitrile and 5 parts sodium styrenesulfonate on the otherside and making up 25 percent of the filament is slickened in the samemanner except from methylene chloride solution and converted into sliverB. Sliver A and sliver B are blended on a pin drafter and spun into a/1cc (531 denier) yarn with 7.12 turns per inch (2.8 turns per cm.)twist. This yarn is knit into a jersey fabric having 16 courses per inch(6.3 courses per cm.) and the fabric is scoured and then dyed at theboil at a pH of 4.5. The resulting fabric is soft and slick, and theslickness is not destroyed by hand abrasion. The bicomponent fibercrimps during the dyeing and results in a bulky yarn.

EXAMPLE lIl Ten parts of the aminosiloxane described in Example 11 aremixed with 489 parts of absolute ethanol and 1.5 parts of thepolyepoxide of Example I added to the solution. The resulting solutionis used to saturate 50 parts of 10 denier per filament staple fiberidentical to that treated in Example 1. After squeezing out the excesssolution so that the solution pickup on the fiber is 100 percent, thefiber is dried by'heating 30 minutes at 70 C. then further heated at 130C. for an additional 30 minutes. The treated fiber is carded and theresulting sliver blended with untreated acid-dyeable high-shrinkagesliver of Example I. The blended fibers are spun into a 6/ Ice (886denier) yarn with 52 turns per inch (1.97 turns per cm.) twist. The yarnis skein-dyed at a pH of 2.5. This causes bulking of the yarn due to theshrinkage of the high-shrinkage fraction and the migration of treatedfibers to the surface. The yarn is knit into a flat fabric and found tobe soft and slick and the finish is durable to hand abrasion.

EXAMPLE IV This example demonstrates the application of a combination ofan aminosiloxane and a polyepoxide from an emulsion.

Part A. 1.9 parts of an emulsifying agent (stearoyl colaminoformyl-methyl pyridinium chloride) are dissolved in 184 parts water bystirring. Then 37.5 parts of a polyepoxide is added slowly withstirring.

Part B. 7.5 parts of an emulsifying agent (stearoyl colaminoformyl-methyl pyridinium chloride) are dissolved in 1,470 parts of waterwith stirring and there is then added a solution of 150 parts of theamino siloxane of Example 11 in 150 parts of isopropyl alcohol.

Parts A and B are then mixed with stirring and the resulting emulsion isused for treating a tow of an acrylic fiber spun from a polymer made bycopolymerizing 88.9 parts acrylonitrile, 5.4 parts of methyl vinylpyridine, and 5.7 parts methyl acrylate by passing the tow overapplicator rolls. The rate of application is such that 3 percent ofsiloxane is applied to the fiber on a dry weight basis. The tow is nextcut into staple fiber and dried at 130 C. for 30 minutes. This fiber iscarded to yield Sliver A. This is blended with slivers of some of brokenon the Turbo Stapler to give high-shrinkage Sliver B which was nottreated according to the present invention. A 70/30 blend of Sliver Aand Sliver B are spun into a 6/lcc (886 denier) yarn with 52 turns perinch (2 turns per cm.) twist. The yarn is wound into skeins and dyed 2hours at the boil at a pH of 2.5 using acid colors. This yarn is knit ona Stoll JBO Flat Bed Machine into a two-color welt construction. Eventhough the finish is subjected to rigorous process conditions, includingscouring and dyeing, during the necessary steps to convert tow intofabrics, the final fabric is soft and slick and it retains theseproperties through at least five home laundry cycles.

The relative coefficient of friction f for the treated fiber and for theuntreated fiber is determined as follows:

A flat, horizontal plane is covered with carded staple fiber to betested. A weighted aluminum block covered with emery cloth is placedupon the fiber-covered surface. The block is attached to a strain gaugeand the force required to move one with relation to the other ismeasured. The fiber-to-fiber friction is measured. The values fortreated and untreated unblended staple are 0.1 10 and 0.184,respectively. The significant difference in the measurement is 0.02.

EXAMPLE V This example demonstrates the application ofaminosiloxane/polyepoxide to a polyester fiber.

A solution is prepared by adding 8 parts of the aminosiloxane of Examplell and 1.2 parts of polyepoxide to 790 parts ethanol. Seventy-sevenparts of semi-dull staple fibers of 3 denier and a cut length of 1.5inches (3.8 cm.) spun from poly(ethylene terephthalate) are dipped intothe solution and the excess solution squeezed out to leave a percentpickup of solution on the dry weight of the fiber to deposit 1 percentof aminosiloxane on the fiber. The staple fiber is dried and cured 30minutes at C. and spun into a l0/cc (531 denier) 14 turns per inch (5.5turns per cm.) yarn. The yarn is knit into a 16 stitch per inch (6.3stitch per cm.) jersey fabric. This fabric is dyed with a dispersedyestuff at the boil at a pH of 5.5. The resulting fabric is much softerand slicker than a similar fabric made from fibers which have not beentreated with aminosiloxane-polyepoxide.

EXAMPLE VI The example demonstrates the use of a combination of anepoxysiloxane and a diamine as a fiber finish.

Eight parts of epoxysiloxane having 5 percent epoxy group and aviscosity of 700 CSTKS and 1.6 parts of 1,6-diaminohexane are dissolvedin 390 parts of absolute ethanol. One hundred parts of the basic-dyeablestaple fiber of Example ll are dipped into this solution and the excesssolution squeezed out to leave 100 percent wet pickup. The fiber is thencured 30 minutes at 130 C. and then spun into a l0/cc (531 denier) 7.1Zturns per inch (2.8 turns per cm.) yarn. This yarn is knit into a 16stitch/inch (6.3 stitch/cm.) jersey fabric and dyed at a pH of 4.5 withbasic cationic dyes. After scouring and drying, this fabric has a soft,slick hand which is retained through many launderings and repeatedabrasions.

EXAMPLE Vll This example demonstrates the application of a combinationof an epoxysiloxane and an aminosiloxane to a fiber from an emulsion.

Part A. 33.3 parts of the epoxysiloxane of Example V1 are dissolved in333 parts of isopropyl alcohol and the resulting solution poured slowlyinto a solution of 1.7 parts of the emulsifying agent of Example 1V in600 parts of water with stirring.

Part B. 16.7 parts of the aminosiloxane of Example 11 are dissolved in16.7 parts isopropyl alcohol and the resulting solution poured withstirring into a solution of 0.8 parts of the above-emulsifying agent in300 parts water.

Parts A and B are thoroughly mixed and immediately applied to a tow ofan acrylonitrile polymer fiber comprising a terpolymer of 88.8 parts ofacrylonitrile, 5.8 parts of methyl acrylate, and 5.4 parts of2-methyl-5-vinyl pyridine so as to leave 2 percent of the total siloxaneon the fiber, based on the dry weight of the fiber. This tow is then cutinto staple and heated 30 minutes at 130 C. to bring about the reactionbetween the amino groups and the epoxy groups. The staple fiber isdecidedly softer and slicker than an untreated fiber.

Seventy-seven parts of this staple fiber are blended with 33 parts of astaple fiber of the same chemical composition but having been broken onan apparatus, described in US. Pat. No. 2,748,426, for stretch-breakingtow into staple fiber (manufactured and sold under the tradename TurboStapler by the Turbo Machine Co. of Lansdale, Pa.) to give a highshrinkage of over 30 percent. The blended fibers are next spun into a6/cc (886 denier) yarn with 52 turns per inch 1.97 turns per cm.). Thisyarn is two-plied, wound into skeins and dyed with acid colors at a pHof 2.5. The dyed yarn is knit into a two-color welt construction. Thefabric possesses a durable, soft, slick hand.

EXAMPLE VIII This example demonstrates finishing a fiber with thereaction product of an epoxysiloxane and a polyoxy propylene diamine.

Fifty-four parts of an epoxysiloxane having 5 percent epoxy group aredissolved in 3,920 parts of ethanol containing 27 parts of apolyoxypropylene diamine with a DP of about 400. The resulting solutionis used to treat 1,000 parts of an acrylonitrile polymer fibercomprising a terpolymer of 88.8 parts of acrylonitrile, 5.8 parts ofmethyl acrylate, and 5.4 parts of 2-methyl-5-vinyl pyridine. The excesssolution is pressed from the fiber leaving a 100 percent wet pickup. Thefiber is next heated for 30 minutes at 130 C. The resulting fiber isspun into a 6/cc (886 denier) yarn with 52 turns per inch (2 turns percm.). The yarn is two-plied, skeined, and dyed with acid dyes at a pH of2.5. It is next knit into a twocolor welt construction. The fabric hasthe slick, soft feel of mohair. This feel is durable to hand abrasionand to laundering.

EXAMPLE IX This example demonstrates the treatment of a fabric by thisinvention.

An acrylic fiber of 10 denier per filament is spun from a ter polymer of92.2 parts acrylonitrile, 5.4 parts methyl vinyl pyridine and 2.4 partsmethyl acrylate. The fiber in the form of a tow is broken on a TurboStapler. Part of the fiber is heat-set with steam and has a lowshrinkage. That which is not heat-set has a shrinkage of at least 30percent. Seventy parts of the low shrinkage fiber in the form of sliveris blended with 30 parts of high shrinkage sliver. Blending is onspinning frame. The final sliver is spun into a 6/cotton count (886denier), 5 turns per inch (1.97 turns per cm.) Z twist yarn. This yarnis knit into a two-color welt construction on a Stoll JBO Bed KnittingMachine.

Twenty-five parts by weight of this fabric are treated with a solutionof 2 parts of the aminosiloxane of Example 11 and 0.3 parts ofpolyepoxide in 198 parts of absolute ethanol. The fabric is squeezed toremove excess solution and leave 100 percent solution on the fiber. Itis next dried and heated 30 minutes at 130 C. The resulting fabric isfound to be pleasantly soft and slick. Fabrics from other fibers can betreated likewise.

EXAMPLE X This example demonstrates the use of an in-line mixing processfor preparing the finish for application to the fiber.

The aminosiloxane and the polyepoxide of Example 11, a surface activeagent (trialkyl polyoxyalkylene quaternary ammonium chloride) and waterare fed into a Gifford-Wood 2- inch (5.08 cm.) Pipeline Homomixer in aratio of 1 part aminosiloxane, 0.25 part polyepoxide, 0.03 part surfaceactive agent and 14 parts water, all by weight. The resulting dispersionis pumped continuously onto a moving tow of 87,500 denier spun from aterpolymer 88.9 parts of acrylonitrile, 5.4 parts methyl vinyl pyridineand 5.7 parts methyl acrylate. The tow is cut into 4.5 inch (11.4 cm.)staple and the staple is heated 30 minutes at 130 C. The staple is nextconverted into sliver and 77 parts of this sliver are blended on a pindrafter with 33 parts of sliver of composite fiber spun from twopolymers in side-by-side relation along the length of the fiber, PolymerA being a mixture of 84 parts of a polymer from percent acrylonitrileand 16 parts of a copolymer of 95.8 percent acrylonitrile and 4.2percent sodium styrene sulfonate, and Polymer B being a copolymer of95.8 percent acrylonitrile and 4.2 percent sodium styrene sulfonate.

The final blended sliver is spun into a 6/1cc (886 denier) yarn with 5.0Z turns per inch (2 turns per cm. This yarn is two-plied with 2.5 Sturns per inch (1 turn per cm.). The plied yarn is skien dyed and knitinto a two-color welt construction. The fabric is pleasantly soft andslick and retains these properties after repeated launderings.

EXAMPLE XI This example demonstrates the application of the finish ofthis invention to a composite two-component fiber.

A staple fiber of 3.5 denier per filament and 3 to 3.5 inch (7.6 to 8.9cm.) length is spun from two different polymers to yield a compositefiber. One polymer component (polymer A) is a terpolymer of 93.6 partsacrylonitrile, 6.0 parts methyl acrylate and 0.4 part sodium styrenesulfonate. The other component (Polymer B) consists of 90 parts ofacrylonitrile polymer and 10 parts of Polymer A. The composite fibercontains approximately equal amounts of Polymer A and Polymer B inside-by-side relation along the length of the fiber.

Two hundred twenty-five parts of this staple fiber are treated with asolution of 40 parts of the aminosiloxane of Example II and 6.0 parts ofthe polyepoxide of Example II in 1,954 parts of isopropyl alcohol. Thestaple is partially freed of solution by squeezing then dried 20 minutesat 140 C. to fix the finish on the fiber. The treated staple is cardedand spun into a 6/1cc (886 denier) yarn with 5.5 Z turns per inch (2.2turns per cm.). This yarn is two-plied with 2.8 S turns per inch (1.1turns per cm.) and knit into a half cardigan construction. Afterscouring and dyeing 1.5 hours, at the boil, the resulting fabric has asoft, smooth feel.

EXAMPLE XII .speed, followed by 4.5 parts of the polyepoxide used inExample I. The resulting mixture, which contains 30 percentaminosiloxane and 4.5 percent polyepoxide, is diluted with water to forman emulsion containing only 2 percent of the aminosiloxane. The 2percent emulsion is used to treat parts of a staple fiber made bydry-spinning from solution in dimethyl forrnamide a polymer of 96 partsof acrylonitrile and 4 parts of sodium styrene sulfonate. The squeezingpressure employed during application is such that the pick-up ofemulsion on the fiber is 100 percent on the weight of the fiber. Thestaple fiber is then heated for 30 minutes at C. to evaporate water andcure the finish on the fiber. After the curing step, the fiber is spunin a blend with 30 percent of a staple fiber made of a polymer of 88.9parts of acrylonitrile, 5.4 parts methyl vinyl pyridine and 5.7 parts ofmethyl acrylate, but containing no silicone finish, to a 6'cc. yarnhaving 52 turns per inch twist. The yarn is plied and dyed at a pH of2.0. The

dyed yarns are knitted to fabric. The resulting knitted fabrics arerated as very slick.

EXAMPLE XIII Into a 2-inch (5.08 cm.) pipeline mixer (commercially 5available as a Gifford-Wood pipeline homomixer) is fed a mixture of1,870 parts of water, 67.6 parts of the polyepoxide of Example I, 338parts of the aminosiloxane of Example II, and 7.2 parts of a surfaceactive agent comprising a polyoxyalkylene derivative of a secondaryalcohol (commercially available surface active agent identified asTergitol 13-S-12). The resulting dispersion is pumped continuously ontoa moving tow of 450,000 denier of an acrylonitrile polymer fibercomprising a terpolymer of 88.8 parts of acrylonitrile, 5.8 parts ofmethyl acrylate, and 5.4 parts of 2-methy1-5-vinylpyridine. The tow isdried and cured continuously by passing through an oven at a rate toprovide 8.2 minutes residence in an environment at 135 C. The tow is cutinto staple fibers 3 inches long and the staple is scoured for 1 hour atthe boil in a 0.5 percent aqueous solution of a commercially availablesurfactant (identifiedas Igepal CO-SSO) acidified to a pH of 2.5 withsulfuric acid. The staple fibers are rinsed and dried. A plot isprepared of the coefficient of friction of the fibers, with respect tothe sliding speed at which the measurement is made. This coefficient offriction plot is shown in FIG. 1. The Objective Preference Index of thisfiber, calculated as hereinbefore described, is 0.94.

Similar plots of the coefficient of friction, with respect to thesliding speed at which the measurement is made, are prepared and thecorresponding Objective Preference Indexes are calculated for thefollowing fibers: an untreated sample of the same acrylonitrile polymerstaple fiber employed in the above paragraph; a commercially availablesample of alpaca fiber; a commercially available sample of mohair fiber;an acrylonitrile polymer staple fiber bearing a cured coating ofepoxysilicone and 1,4-diaminobutane, prepared as described below; and anacrylonitrile polymer staple fiber bearing a cured coating of a siliconecontaining silyl hydrogen atoms mixed in admixture with a solublepolyepoxide, and analyzing 2.06 percent silicone. The ObjectivePreference Indexes calculated for these fibers are given in Table 1, thefibers being listed in the same order described. The curves for all ofthese fibers are shown in FIG. 2. It will be noted that the fiber of theinvention, bearing the cured aminosiloxane-epoxy coating, is verysimilar in shape to the curves obtained with the natural alpaca andmohair fibers, in that the initial coefficient of fraction is relativelylow and dips slightly lower to a minimum as the sliding speed isincreased, then rises very sharply and progressively as the slidingspeed is further increased. The untreated acrylonitrile polymer staplefiber has a high initial coefficient of friction which decreasessomewhat as the sliding speed is increased. The acrylonitrile polymerstaple fibers bearing cured coatings of other silicones have low initialcoefficients of friction as contrasted with the untreated acrylonitrilepolymer staple fibers; but the curves do not rise as the sliding speedincreases, so that the coefficients of frietion are low regardless ofspeed.

The next-to-last item in Table l is prepared by applying a mixture of 4cc. of 0.40 g. of a dlmethyl polysiloxane having 1 percent pendantepoxide groups and a viscosity of 4,0008,000 centistokes in 40 cc. ofbenzene and 4 cc. of a solution of 0.01 g. of 1,4-diaminobutane in 40cc. of benzene to 2.0 g. of a 9 denier per filament, 3-inch staple fiberof the same acrylonitrile polymer described in the first paragraph ofthis example. After evaporation of the solvent, the staple is cured 15minutes at 135 C. and then scoured 1 hour at the boil as in the firstparagraph of this example, rinsed, and dried.

EXAMPLE XIV Solutions of the following materials are made in 40 cc. ofbenzene:

A. 0.32 g. of the aminosiloxane described in Example 11 B. 0.28 g. ofthe aminosiloxane described in Example II C. 0.24 g. of theaminosiloxane described in Example 11 D. 0.08 g. of the polyepoxide ofExample I E. 0.12 g. 1,3-bis-( 3-glycidoxypropy1)tetramethyldisiloxaneF. 0.16 g. resorcinol diglycidyl ether To 2 g. of unmodified 9 denierper filament staple fibers of a terpolymer comprising 88.8 partsacrylonitrile, 5.8 parts methyl acrylate, and 5.4 parts of2-methy1-5-vinylpyridine in a beaker is added a mixture of 4 cc. ofsolution (A) and 4 cc. of solution (D) above, and the mass of fibers isworked to distribute the applied solution as evenly as possible. Thebenzene is allowed to evaporate at room temperature, and the sample isthen cured 15 minutes at 135 C. in a forced draft oven. The procedure isrepeated for a mixture of solution (B) and solution (E); and repeatedagain for a mixture of solution (C) and solution (F). Each of thesamples of cured fibers is then scoured at the boil for one hour in asolution of 0.5 percent of a commercially available surfactant(identified as Igepal CO-880) acidified to a pH of 2.5 with sulfuricacid. After thorough rinsing, the samples are dried at room temperatureand their frictional characteristics are evaluated by calculation ofObjective Preference indexes. The results are given in Table 2.

An aqueous dispersion of a coating composition is prepared from 163.4 g.of water, 0.6 g. of a commercially available dispersing agent(identified as Tergitol 15-8-12), 6.0 g. of the polyepoxide of ExampleI, and 30.0 g. of the aminosiloxane described in Example 11. Theseingredients are added in the order listed into a commercially availableblending apparatus (Waring Blendor) and are agitated at high speed untilemulsified (approximately 3 minutes). The resulting emulsion is dilutedto 0.66 percent silicone with water and applied to un- I treated 9denier per filament staple fibers of a terpolymer comprising 88.8 partsacrylonitrile polymer, 5.8 parts methyl acrylate, and 5.4 parts of2-methyl-5-vinylpyridine to give a 2 percent coating on the fibers. Thefibers are mixed thoroughly in a beaker, and the wet, coated staple isthen dried and cured in a forced draft oven at 135 C. for 15 minutes.The cured fibers are then scoured at the boil for one hour in a solutionof 0.5 percent of a commercially available detergent (identified asIgepal CO-8 acidified to a pI-I of 2.5 with sulfuric acid.

The procedure described in the preceding paragraph provides a fiberhaving a cured coating containing 20 percent of the polyepoxidecrosslinking agent, based on the weight of the aminosilicone. Thisprocedure is repeated, employing various proportions of the ingredients,and the frictional characteristics of the fibers are evaluated bycaiculation of Objective Preference Indexes. The results are given inTable 3.

TABLE 3 Vt eight Weight Amincsilkone Polyepoxide (g.) Polyepoxide P133.0 g. 3.0 g. 9 0.89 30.0 6.0 20 0.97 27.0 9.0 33 0.79 24.0 12.0 500.81

EXAMPLE XVI Solutions of the polyepoxide of Example I in variousamounts, as shown in Table 4, are made up in 40 cc. of benzene each. Asolution of 0.32 g. of the aminosiloxane of Example ll having an aminecontent of 1.8 percent of 40 cc. of benzene is also prepared, togetherwith similar 40 cc. benzene solutions of aminosiloxanes having aminecontents of 0.4, 1.0 and 6.0 percent (aminosiloxanes supplied by UnionCarbide Corp., designated Y-6165, Y-5477, and Y-5078 respectively) asshown in the table and in the amounts indicated therein. Mixtures of 4cc. of the aminosiloxane solutions with 4 cc. of the correspondingpolyepoxide solutions are applied to 2.0 g. portions of untreated9-denier per filament staple fibers of a terpolymer comprising 88.8parts of acrylonitrile, 5.8 parts of methyl acrylate, and 5.4 parts of2-methyl-5-vinylpyridine. The fibers are mixed thoroughly in a beaker,and the wet, coated staple is then dried, cured, and scoured as inExample XV. The frictional characteristics of the fibers are evaluatedby calculation of Objective Preference Indexes, and the results aregiven in Table 4.

Based on total weight of coating The fiber having the coating containing6.0 percent amine and 45 percent polyepoxide, although slicker thanunmodified fiber, has a low OPI value and resembles the natural luxuryanimal fibers less than the other fibers do.

EXAMPLE XVII A mixture of 87.5 g. of the aminosiloxane of Example 11 and1.75 g. of a commercially available dispersing agent (identified asTergitol 15-S-l2) is made and 204 m1. of water is added slowly withvigorous stirring to produce a 30 percent emulsion of the aminosiloxanein water. To this is added, in

order, 9 ml. of glacial acetic acid, 17.5 g. of the polyepoxide ofExample I and 3,189 ml. of water to produce an emulsion containing 2.5percent of the aminosiloxane. The emulsion is applied to a 30,000 denierrope of polyethylene terephthalate polymer fiber of 8 denier perfilament by dipping the rope into the emulsion and wringing off excessuntil the emulsion pickup is 20 percent based on the ropes dry weight.The rope is then crimped in a stufier-box crimper and dried and heatedfor 8 minutes by passage through a forced-draft oven at 135 C. tocross-link the surface modifier and relax and crystallize the fiber. Atextile finish to provide acceptable textile processibility is appliedto the dried, cured rope, and the rope is then cut to 4.5-inch staplefiber. The staple analyzes 0.68 percent aminosiloxane, based on dryfiber weight. The staple is scoured 1 hour at the boil in a 0.5 percentaqueous solution of a commercially available surfactant (Igepal CO-880)acidified to pH 2.5 with sulfuric acid, rinsed, and dried. A controlfiber is prepared in the same way except that 20 percent water isapplied in place of 20 percent aminosiloxane emularm sion. The surfacemodified fiber has an 0P1 of 1.64, as contrasted with an 0P1 of 0.40 forthe control. The tactile softness and slickness of knit fabrics madeusing the surface modified fiber is very pleasing to the hand, andsimilar to the handle of mohair, whereas the fabric knit from thecontrol fiber lacks the mohair-like hand. The friction plots of thetreated and untreated polyester fibers of this example are shown in FIG.3.

EXAMPLE XVIII Yarns unraveled from the fabrics prepared in Examples 1-V,VII, X1, and X11 are examined for their frictional characteristics in amodification of the test described above for calculation of theObjective Preference Index. In the modified test, the cardboard tubesare covered with several layers of the yarns unraveled from the fabricsand the 1X9-inch strip of one-sided pressure-sensitive plastic tape iscovered with closepacked, parallel yarn arrays. Plots of the coefficientof friction of the yarns, with respect to the sliding speed at which themeasurement is made, are prepared and the Objective Preference Index iscalculated as previously described. It is noted that the values for theObjective Preference Index of the yarns are lower than the correspondingvalues for the staple fibers, although the shapes of the curves aresimilar. For example, the shape of the curve for the control sample ofpercent mohair yarn is similar to the shape of the curve for 100 percentmohair staple fibers, but the 0P1 for the mohair yarn is only 0.53 ascompared with 1.03 for the mohair fibers. Similarly, the yarn unraveledfrom the fabric of Example 11, made of aminosiloxane-epoxy coatedpolyacrylonitrile fibers prepared in accordance with the invention, hasan OPl of only 0.50 as compared with an OPI of 0.94 for the similaraminosiloxane-epoxy coated polyacrylonitrile staple fiber shown in Table1, although the shape of the curves are similar. The results obtainedwith the yarns are given in Table 5.

TABLE 5 0P1 of Yarn Unraveled I claim:

1. A synthetic organic textile fiber having a coating compositionselected from the group consisting of:

l. a cured mixture of about 0.05 to 3 parts by weight of a soluble epoxycompound having at least 2 epoxy groups per molecule, together with 1part by weight of a liquid arninosiloxane wherein there is one oxygenatom bridging each pair of neighboring silicon atoms and all othersilicon valences are bonded only to carbon atoms, said arninosiloxaneconsisting essentially of repeating units of the formulae:

L ll

wherein R is a lower alkyl or aryl group, R is hydrogen or a lower alkylor aryl group,

A is an alkylene group having two to five carbon atoms or an arylene orsubstituted arylene group having six to carbon atoms, provided R and Aare selected so that not more than one aromatic ring is attacheddirectly to the ammo nitrogen atom,

said aminosiloxane containing at least 35 of said repeating units, atleast two of which have the formula:

2. a cured mixture of about 0.3 to 20 parts by weight of a liquidepoxysiloxane in each molecule of which there is one oxygen atombridging each pair of neighboring silicon atoms and all other siliconvalences are bonded only to carbon atoms, said epoxysiloxane moleculeconsisting essentially of repeating units of the formulae:

and

together with 1 part by weight of an amine compound having at least twoamino groups per molecule wherein each of said amino groups has at leastone hydrogen atom and not more than one aromatic ring attached directhto the aiitacgmnzamd 3. a curled admire of'aimut (L155 a: 20 parts byweight of said epoxysilbxane together with 1 part by weight of saidaminosiloxane;

said coating composition being present in an amount suffi- I cient toprovide the fiber with an improved, durable, soft,

lubricated feel.

2. The fiber of claim 1 wherein said fiber comprises an acrylonitrilepolymer.

3. The fiber of claim 2 wherein said composition is selected from thegroup consisting of l) a cured mixture of said epoxy compound and saidaminosiloxane and (2) a cured mixture of said epoxysiloxane and saidaminosiloxane.

4. The fiber of claim 3 wherein said composition is a cured mixture ofsaid epoxy compound and said aminosiloxane wherein said aminosiloxanecontains to 600 of said repeating units, four to 20 of which are unitsof the 5. A textile fiber of claim 1 wherein said composition isselected from the group consisting of (l) a cured mixture of said epoxycompound and said aminosiloxane and (2) a cured mixture of saidepoxysiloxane and said amino siloitane.

2. The fiber of claim 1 wherein said fiber comprises an acrylonitrilepolymer.
 2. a cured mixture of about 0.3 to 20 parts by weight of aliquid epoxysiLoxane in each molecule of which there is one oxygen atombridging each pair of neighboring silicon atoms and all other siliconvalences are bonded only to carbon atoms, said epoxysiloxane moleculeconsisting essentially of repeating units of the formulae:
 3. a curedmixture of about 0.05 to 20 parts by weight of said epoxysiloxanetogether with 1 part by weight of said aminosiloxane; said coatingcomposition being present in an amount sufficient to provide the fiberwith an improved, durable, soft, lubricated feel.
 3. The fiber of claim2 wherein said composition is selected from the group consisting of (1)a cured mixture of said epoxy compound and said aminosiloxane and (2) acured mixture of said epoxysiloxane and said aminosiloxane.
 4. The fiberof claim 3 wherein said composition is a cured mixture of said epoxycompound and said aminosiloxane wherein said aminosiloxane contains 100to 600 of said repeating units, four to 20 of which are units of the 5.A textile fiber of claim 1 wherein said composition is selected from thegroup consisting of (1) a cured mixture of said epoxy compound and saidaminosiloxane and (2) a cured mixture of said epoxysiloxane and saidamino siloxane.